Dye intermediates and derived azo dyes



Patented Aug. 16, 1932 UNrrsD s A'iEsS ERNEST F. GRETHER, or MIDLAND,MICHIGAN, ASSIGNOR TO THE Dow CHEMICAL coivirANY, on MIDLAND, NIcHIeAN,A CORPORATION or MIcIIIeAN DYE INTERMEDIATESAND-DERIVED AZO DYES NDrawing.

My invention relates to new azo-arylide derivatives of hydroXy-aromaticcarboxylic acids, more particularly to such derivativesof2z3-hydroxynaphthoic acid, and to directdeveloped poly-azo-dyesderived therefrom by coupling with suitable diam-components.

The dye intermediates of my invention belong-to-thc general classofazo-arylid'es of hydroxyearomatic carbo-Xylic acids,

which maybe coupled suitable diazo-com ponents with the consequentproduction of the so-called ice-colors or direct-developed dyes; In, apending application, Serial No.

358,756, filedApril 27, 1929', I have described new azo-arylid'es of2;3-hydr0xynaphtho1c the aforesaid azo-arylides being formed bycondensing awith said acid in equimolecular proportioni In a laterapplication, Serial No. 3743284, filed June 27, 1929, I have describedrelated azo-arylides, made by condensing one mole of a diaminoazo-compound with two moles of the abovementioned acid, and also amdyesderived therefrom.

A I have now foimd that complex azo-arylidesof related character may beprepared by condensing" a conjugated diamino-azo compound of the generalformula, v i NH RN= N,R-J NH wherein R and R are ai'yl residues, withtwo moles of a hydroxynaphthalene cart-- boitylic acid, e. g-,.

pounds are composed of two aromatic nuclei joined thru an azo" group,each of. thearomatlc nuclei carrying one-ormore lhe azo-arylidecompoundsamino groups. m so-produced constitute new anduseful intermediateproducts from which azo-dyes of excellent fastness to light and washingmay be prepared by coupling with suitable diazotized or poly-azotizedaromatic '1 amino compounds. The invention, then, consists of theaforesaid new intermediate compounds and azo-dyes derived therefrom,together with methods for the; preparation thereof, as hereinafterdescribed and par-" witicularly pointed out in the claims, the fol-Application filed July 25,

into

acidand new azc-dyes derived therefrom,

monoaminonae-compound 2Q3hydroxynaphthoic acid.- Such conjugated'diamino-azo-com 1929. Serial No. 381,087.

lowing description setting forth detailed procedure'representative ofvarious ways in which the principle of the invention may be used; A

f. The'herein described new intermediate compounds, comprising poly(hydroxy naphthoyl) derivatives of diammo aromatic azo-compounds, havethe following general formula:"--

wherein Reandi represent aryl residues which: may 'be eitherthe' same ordifier entg andieit'hen one orboth may be further substituted or not',as desired, by*=-other monova- I lent groups, such as--ha1 gen; nitr o,azo 7 groups, etc. The aforesaid groups R and R may be mono-nuclear,poly-nuclear, con--- densed-nuclear, or conjugated-nuclear, such as'theresidues fromcompounds ofthe benz ene, di-plienyl, naphthalene ordi-aryl ether ful pigments, or in any other referred manner. H

A preferred mode of procedure for. carryingout the invention isillustrated in the fllowiirg examples, but it is un'derstdodithatsuch'examples are not to be interpreted- 21s a limitation upon theinvention.

Emma A One molepeamino-acetanili'de is diazoti' z ed" and coupled withone mole alphanaphthyl- IQQ,

' amine. The azo-product is. hydrolyzed to remove the acetyl group, andthen condensed with two moles 2.3-hydroxynaphthoic acid bio : ably hasthe formula formula by heating the two compounds dissolved or suspendedin toluene, or other suitable me- 'dium, wit h addition of asmall'amount of phosphorus trichloride, the heating being carried outunder reflux for approximately 7 threeto five hours. The reactionmixture is then neutralized with sodium carbonate and the toluenedistilled off with steam. The desired compound remains in suspension inthe residual aqueous liquid and is filtered therefrom and water-washed.Tlie product is purified by dissolving'in dilute (one to two percent)caustie alkali solution, filtering from unreacted diamineandrep'recipitating by acidification of the alkaline solution. Theintermediate compound so produced prob- Cotton niaterial;,;isimpregnated with a slightly alkaline solution ofthe above intermediatecompound towhich asmall amount of formaldehyde may advantageously. beadded and, if desired, turkey red oil orotherl agent to facilitate theabsorption of the solution by oron the fiber. The impregnated ma terialis then immersed in a cold solution of, sodium acetate or carbonate andthe dye de-;

veloped by adding a diazo solution prepared from two molesalpha-naphthylamine. .The color is purple.

The dyeprobable has the g 7 Example 2 In similar manner to Example 1,two moles o-chloro-p-toluidine are diazotized and coupled into the samecomplex arylide. The resulting dye is scarlet in color and probably hasthe formula 2+ In a similar fashion other dyestuffs have:

been prepared bycoupling other diazotized': or tetrazotized amino orpoly-amino aromatic compounds withthe same or other hydroxy compounds ofthe type above described. i

Among, the diam-components employed, may

be mentioned; m -nitraniline, pamino-acetanilide,t/F-diaminmdiphenylether, benzidine and p-nitro-benzene-azo-o-toluidine, 9

Although in Example 1, cotton fiber is specifically referred to as thematerialleultion which the present dyes may be developed, my

new dyes are also capable of dyeing-other" natural or v syntheticfibers,such as ;.w.ool', silk,-

rayon, or the like..

The present dyestuffs may be applied upon the fiber or not, as desired;the invention being independent of the. particular modeeof applicationemployed. Auxiliary treatments for fixing orotherwise aiding theabsorption 2 of the dye by or on the fiber may be utilized E optionallyin conjunction with the dyeing:

process without departing from the spirit of? the invention whichconcerns not only-the new dyes but also materials dyed therew-ithli.

In carrying out;the .invention; for produc--- aazrm therefrom, thelatter being characterized by.

the following grouping wherein R and R represent aryl residues, andwherein the several groups and residues may be further substituted.

Other modes of applying the principle of my invention may beemployedinstead of the one explained, change being made as. regards the steps ormaterials employed, provided the steps or ingredients stated by any ofthe following claims or the equivalent of such stated steps oringredients be employed.

I therefore particularly point out and tinctly claim as my invention2-- 1. The method of making new azo-compounds which comprises condensinga diamino aromatic azo-compound having the general formula, NH -RN=NR NHwherein R and R represent aryl residues of the benzene and/ ornaphthalene series which. may bear substituents' selected from the:group consisting of halogen and nitro' substituents, with2.3-hydroxynaphthoic acid in the approximate proportion of one mole oftheformer to twomoles of the-latter and in the presence of a condensing,agent.

2. The method of making new azo-compounds which comprises condensing adiamis disbenzene; or naphthaleneseries', which residue and naphthalenenucleus may bear substituents selected from the group consisting ofhalogen and nitro substituents, with 2.3-hydroxynaphthoic acid in theapproximate pros portion of one mole of the former-to two moles of thelatter.

3. As a new compound, the condensation- 7 product of a diamino aromaticazo compound with two molecular equivalents of 2.3-hydroxynaphthoicacid, probably having wherein R represents an aryl residue ofthe I thegeneral formula benzene and/or naphthalene series, and the severalgroups and residues may bear substit uents selected from the groupconsisting of halogen and nitro substitu'ents.

4. The method of making new azo-dyes which comprises coupling apoly-(2.3-hydroxynaphthoyl) azo-arylide of the general formula 5. As anew compound, an azodye having 1 the general formula wherein R and Rrepresent aryl residues of the benzene and/ or naphthalene series, Zrepresents: the residue of a diazotized aromatic amino1comp=ouned,.n isthe integer 1 or 2, and wherein the several groups and residues may bearsubstituents selected from the group consisting of halogen and nitrosubstituents.

6: As a new compound, an azo dye having the general formula NBC 0-wherein Z represents the residue of a diazotized aromatic aminocompound, n is the integer 1 or 2, and wherein the several groups andresidues may bear substituents selected from the group consisting ofhalogen and nitro substituents.

7 As a new compound, an azo dye having the general formula wherein Zrepresents a residue of a diazotized aromatic ammo compound and n 1s themteger l or 2.

9. As a new compound, the condensationproduct of a diamino-aromaticazo-compound with two molecular equivalents of 2.3-hydroxynaphthoicacid, said 7 condensation product having probably theformula wherein theseveral groups and residues may bear substituents selected from thegroup consisting of halogen and nitro substituents. 10. As a newcompound, the condensation product of4.4J-diamino-1.1-phenyl-azonaphthalene with two molecular equivalents of2.3-hydroxynaphthoic acid, saidcondensation product having probably theformula OH HO- O ONHON=N8HNO C- 11. The method of making a new azocompound, which comprises condensing a diam;

ino aromatic azo compound having probably the formula v "H,N ON=Nwherein the phenyl and naphthyl residues may bear substituents, selectedfrom the group consisting of h'alogen and nitro substituents, with ahydroxynaphthoic acid in the presence of a condensing agent, therebyforming a compound having'the general formula wherein the several groupsand residues may bear substituents selected from the group consisting ofhalogen and nitro substituents.

12. The method of making new azo dyes 'which comprises coupling apoly-(2.3-hydroxynaphthoyl) azo-arylide having probably the formulawherein the several groups and residues may bear substituents selectedfrom the group consisting of halogen and nitro substituents, with adiazotized aromatic amino compound.

13. As a new compound, an azo dye having the general formula OH HOwherein It and R PQDIQMt My] raidua oi the benzene and/ or naphthaleneseries, which residues may bear substituents selected from the groupconsisting of halogen and nitro substituents, Z represents the residueof a diazotized aromatic amino compound, and n is the integer 1 or 2.

14. As a new compound, the condensation product of a diamino-aromaticazo-compound' with two molecular equivalents of 2.3-hydroxynaphthoicacid, said condensation product h aving the general formula wherein Rand R represent aryl residues ofthe benzene and/or naphthalene series,which residues may bear substituents selected from the group consistingof halogen and nitro substituents.

Signed by me this 23rd day of July, 1929.

ERNEST F. GRETHER.

Certificate of Correction Patent No. 1,871,515. August 16,1932.

ERNEST F. GRETHER It is hereby certified that error appears in theprinted specification of the abovenumbered patent requiring correctionas follows: Page 2, line 53, for probable read probably; page 4, lines126 to 130, claim 13, strike out the formula and insert instead:

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 25th day of October, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Commissioner of Patents.

